CN106496841A - A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing and preparation method thereof - Google Patents
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing and preparation method thereof Download PDFInfo
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- CN106496841A CN106496841A CN201610872237.8A CN201610872237A CN106496841A CN 106496841 A CN106496841 A CN 106496841A CN 201610872237 A CN201610872237 A CN 201610872237A CN 106496841 A CN106496841 A CN 106496841A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2203/18—Applications used for pipes
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to a kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing and preparation method thereof, the tubing is made up of following raw material by mass fraction：100 parts of polyvinyl chloride；15～30 parts of modified nano calcium carbonate；8～15 parts of vinyl bis-stearamides；4～17 parts of nitrogen silicon fire retardant；10～23 parts of impact modifier；1～5 part of castor oil acid calcium；1～5 part of organotin；3～8 parts of antioxidant；Wherein, the modified nano calcium carbonate is obtained by nano-calcium carbonate, 3 aminopropyltriethoxywerene werenes, stearic acid, melamine resin reaction, and the oil factor of the modified nano calcium carbonate is 10～20g/100g.The tubing that the present invention is provided has preferable anti-wear performance and fire resistance, and also there is excellent ageing-resistant performance, processing characteristics, mechanical property and compatibility performance etc..
Description
Technical field
The present invention relates to polyvinyl chloride pipeline field, and in particular to a kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nano-calcium carbonate
Plastic pipe and preparation method thereof.
Background technology
With built environment friendly society of China, the needs of Developing Circulation Economy accelerate resource-conserving, environment
The emphasis for being developed into industry development of the major scientific and technological project project such as friendly, sustainable development and energy-saving and emission-reduction.The country exists
The aspect of the research and extension application of environmental protection tubing has started to walk, and has obtained the support energetically of government department.At present, Shanghai
The departments such as non-environmental protection material, construction, electric power, railway, communication have been prohibitted the use of also to promulgate relevant rule with Beijing important place
Fixed.It is anticipated that non-environmental protection tubing building, traffic, communication, electrical network and all large- and-medium size cities application will be by more and more
Restriction, exploitation environmental protection tubing extremely urgent, environment-friendly materials development have the huge market space.
As polyvinyl chloride (PVC) has excellent performance and price advantage, which has become production in five big resins for universal use
One of maximum resin with consumption figure.Global plastic conduit accounts for the 64% of pipeline market within 2014, and the U.S., Japan, Europe etc. are sent out
Higher up to national and regional proportion.PVC is the maximum plastic conduit kind of current whole world consumption, accounts for using total amount
72%, Japanese proportion is up to 90%.The consumption proportion of PVC：Feed pipe 33%；Downcomer 22.3%；Drainpipe
15.7%；Irrigation pipe 5.2%；Electric insulation sleeve pipe 5%；Gas pipe 0.8%；Other tubing account for 17.7%；Wherein tubing and pipe
Part ratio is 8:1.U.S.'s PVC consumption figure highest, next to that the state such as European, Chinese, Japanese, PVC is in predominantly
Position.The country is had made some progress in terms of the exploitation of stabilizer and other environmental protection auxiliary agents, but the selection in environmental protection auxiliary agent,
Also need to make great efforts to be studied in terms of environmental protection tubing formulating, the expressing technique of environmental protection tubing and parameter optimization.
At present, polychloroethylene pipes are in wearability, anti-flammability, environmental protection, pollution-free, resistance to ag(e)ing, processing characteristics, mechanical property
The performance needs such as energy, compatibility are further lifted.Therefore, still need to study a kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nano-calcium carbonate
Plastic pipe and preparation method thereof.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, there is provided a kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nano-sized carbon
Sour calcium plastic pipe, the tubing that the present invention is provided have preferable anti-wear performance and a fire resistance, also have excellent ageing-resistant
Performance, processing characteristics, mechanical property and compatibility performance etc..
Another object of the present invention is to providing above-mentioned abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing
Preparation method.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing, the tubing press mass fraction by following original
Material composition：
Wherein, the modified nano calcium carbonate is by nano-calcium carbonate, APTES, stearic acid, honey
Polyimide resin reaction is obtained, and the oil factor of the modified nano calcium carbonate is 10～20g/100g.
The present invention can give nano-sized carbon from APTES and stearic acid modified nano-calcium carbonate
Sour calcium has excellent compatibility, dispersiveness and stability in polyvinyl chloride；Melamine resin not only can improve nano-calcium carbonate
Compatibility of the calcium in melamine resin and polyvinyl chloride, can also absorb the chlorine that polyvinyl chloride is discharged during processing and use
Change hydrogen toxic gas, advantageously account for because hydrogen chloride discharges and caused environmental issue.The present invention is first with nano-calcium carbonate, 3-
Aminopropyltriethoxywerene werene, stearic acid, melamine resin have prepared a kind of modified nano calcium carbonate for raw material, then will
Modified nano calcium carbonate is applied in the preparation of plastic pipe, significantly improves the anti-wear performance of tubing.
Inventor has found that the oil factor of modified nano calcium carbonate influences whether mechanical property and the anti-wear performance of tubing, modified
The oil factor of nano-calcium carbonate is less, and its addition is more, is got over the anti-wear performance which is the tubing that raw material is prepared
Good, but when the oil factor of modified nano calcium carbonate is less than 10g/100g, although the addition of modified nano calcium carbonate can increase
Greatly, but the mechanical property of tubing can be remarkably decreased, tubing wear and tear when efflorescence also more serious.Only work as modified nano calcium carbonate
Oil factor when being 10～20g/100g, best with anti-wear performance and mechanical property which is the tubing that raw material is prepared.
In the present invention, the particle diameter of modified nano calcium carbonate also influences whether that its compatibility with other materials, modification are received
The too small dispersive property that can cause agglomerated calcium carbonate, affect calcium carbonate powder of the particle diameter of rice calcium carbonate, and the grain of nano-calcium carbonate
Footpath is excessive, and the surface area of calcium carbonate powder can be caused too small, is equally unfavorable for dispersion of the powder in other materials, so as to shadow
Ring the performance to tubing.It is therefore preferred that the particle diameter of modified nano calcium carbonate is 50～100nm, it is further preferable that described change
Property nano-calcium carbonate particle diameter be 60～70nm.
Preferably, the mass ratio of the nano-calcium carbonate, APTES, stearic acid, melamine resin
For 100：9～17：8～25：17～30.
Preferably, the preparation method of the modified nano calcium carbonate is：
During nano-calcium carbonate, stearic acid, melamine resin are added successively to APTES, to be mixed
Transfer the material in mill after uniform, 0.2～0.8h is reacted at a temperature of 120～175 DEG C, then made with extruder extrusion
Grain, obtains final product modified nano calcium carbonate.
Preferably, the molecular weight of the polyvinyl chloride is 5 × 104～11 × 104.
Preferably, the nitrogen silicon fire retardant is made up of magnesium hydroxide, hydroxyl dimethyl silicone polymer, amino silane.In combustion
During burning, magnesium hydroxide is thermally decomposed into magnesia and water, and the water of generation can cause hydroxyl dimethyl silicone polymer and amino silicone
Alkane reacts, and forms one layer of nitrogenated silicon flame-retardant layer in polyvinyl chloride surface, so as to improve the fire resistance of polyvinyl chloride.It is more highly preferred to
Ground, in the nitrogen silicon fire retardant, the mass ratio of magnesium hydroxide, hydroxyl dimethyl silicone polymer and amino silane is 10：33～45：
35～45.
Preferably, the impact modifier is by ethylene propylene diene rubber, nano titanium oxide, nano aluminium oxide, chlorinated polyethylene
Alkene and mica powder reaction are obtained.
Ethylene propylene diene rubber and haloflex have excellent toughness and impact strength, when both add to polyvinyl chloride
In, island structure can be mutually formed in polyvinyl chloride, it then follows elastic body toughening mechanism, so as to reach toughening effect.And nanometer two
There is less size, larger specific surface area, its surface there is abundant hydroxyl official for titanium oxide, nano aluminium oxide and mica powder
Energy degree, dispersed in polyvinyl chloride phase, it then follows crazing toughening mechanism, so as to reach synergy with elastic body toughening, altogether
With the toughness and impact strength that improve polyvinyl chloride；Nano aluminium oxide also has excellent anti-wear performance, can give polychlorostyrene second
The excellent anti-wear performance of alkene.
In the present invention, it is preferred to, the ethylene propylene diene rubber, nano titanium oxide, nano aluminium oxide, haloflex
Portion rate with mica powder is 100：26～37：17～25：83～92：72～93.
In the present invention, the preparation method of the impact modifier is as follows：
Each component is proportionally added in mill, with mill under 145～170 DEG C of temperature conditionss hybrid reaction
0.3～1h, then obtains final product impact modifier with extruder in 145～170 DEG C of extruding pelletizations of temperature.
Preferably, by trisnonyl phenyl phosphite, N, N- diphenyl-para-phenylene diamines, ethanol and aluminum oxide are anti-for the antioxidant
Should be obtained.It is further preferable that the trisnonyl phenyl phosphite, N, the number of N- diphenyl-para-phenylene diamines, ethanol and aluminum oxide
Than for 100：23～39：17～25：41～62.
The present invention selects trisnonyl phenyl phosphite, N, two antioxidant of N- diphenyl-para-phenylene diamines to compound, Ke Yifu
Give the oxidation resistent susceptibility that polyvinyl chloride is excellent, in fired state, trisnonyl phenyl phosphite be heated with alkaline environment, meeting
Decompose and produce phosphorous acid, the phosphorous acid of generation can be oxidized to phosphoric acid, and phosphoric acid and N, N- diphenyl-para-phenylene diamine are in the condition of high temperature
Under polycondensation reaction can occur, form phosphoric acid-N, N- diphenyl-para-phenylene diamine's condensation polymers form one layer of resistance in polyvinyl chloride surface
Combustion layer, may finally give polyvinyl chloride excellent fire resistance, and unnecessary N, N- diphenyl-para-phenylene diamines can also absorb poly-
The hydrogen chloride toxic gas that vinyl chloride is produced during processing and use, advantageously accounts for because hydrogen chloride discharges and caused ring
Guarantor's problem, aluminum oxide have strengthening action, can improve the mechanical strength of polyvinyl chloride；In order to preferably make antioxidant infiltration former
Material surface, also added ethanol in the antioxidant of the present invention.
In the present invention, the preparation method of the antioxidant is：
Trisnonyl phenyl phosphite, N, N- diphenyl-para-phenylene diamines, ethanol and aluminum oxide are proportionally added into reactor
In, mixing speed is 45～60r/min, reacts 0.3～0.7h, obtain final product antioxidant under the conditions of 73～82 DEG C of maintenance system temperature.
The preparation method of above-mentioned abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing, methods described includes as follows
Step：
S1：During nano-calcium carbonate, stearic acid, melamine resin are added successively to APTES, treat
Transfer the material into after being well mixed in mill, 0.2～0.8h is reacted at a temperature of 120～175 DEG C, is then squeezed with extruder
Go out granulation, obtain final product modified nano calcium carbonate；
S2：It is well mixed during modified nano calcium carbonate and other materials are added to reactor, then transfers the material into
In mill, 0.5～1h of hybrid reaction under the conditions of 145～220 DEG C, and extrusion molding under the conditions of 145～220 DEG C, obtain final product
The abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing.
Compared with prior art, the present invention has the advantages that：
The present invention is clicked to change with polyvinyl chloride, modified nano calcium carbonate, vinyl bis-stearamides, nitrogen silicon fire retardant, anti-impact
Property agent, castor oil acid calcium, organic tin stabilizer and antioxidant be raw material, there is provided a kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/receive
The formula of rice calcium carbonate plastics tubing, and various plastic conduits are prepared into by expressing technique.The tubing that the present invention is provided has
Preferably anti-wear performance and fire resistance, also have excellent ageing-resistant performance, processing characteristics, mechanical property and compatibility performance
Deng.
Specific embodiment
With reference to embodiment, the present invention will be further described.These embodiments are only that the typical case of the present invention is retouched
State, but the invention is not restricted to this.In following embodiments, test method used if no special instructions, is conventional method, is made
Raw material, reagent etc., if no special instructions, being can be from the raw material and reagent that routinely commercial sources such as commercial are obtained.
Embodiment 1
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 34 parts of N, N- diphenyl-para-phenylene diamines, 20 parts of ethanol and 53 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 49r/min, 0.5h is reacted under the conditions of 79 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 33 parts of nano titanium oxides, 23 parts of nano aluminium oxides, 87 parts of chlorinated polyethylenes are weighed
Alkene and 86 parts of mica powders are added in mill, with mill in 155 DEG C of hybrid reactions 0.5h of temperature, with extruder in temperature
155 DEG C of extruding pelletizations, obtain impact modifier；
(3) 37 parts of hydroxyl dimethyl silicone polymers are weighed and 41 parts of amino silanes is added in closed container, anti-at 29 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 14 parts of APTESs, 21 parts of stearic acid, 26 parts of melamines are weighed
Resin is added in mill, with mill in 149 DEG C of hybrid reactions 0.4h of temperature, is made in 149 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 65nm, and oil factor is 14g/100g；
(5) 100 parts of polyvinyl chloride, 26 parts of modified nano calcium carbonates, 13 parts of vinyl bis-stearamides, 12 parts of nitrogen silicon are weighed
Fire retardant, 19 parts of impact modifiers, 3 parts of castor oil acid calcium, 4 parts of organic tin stabilizers and 6 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 169 DEG C of hybrid reactions 0.6h of temperature, with extruder in 173 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 2
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 23 parts of N, N- diphenyl-para-phenylene diamines, 17 parts of ethanol and 41 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 45r/min, 0.3h is reacted under the conditions of 73 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 26 parts of nano titanium oxides, 17 parts of nano aluminium oxides, 83 parts of chlorinated polyethylenes are weighed
Alkene and 72 parts of mica powders are added in mill, with mill in 145 DEG C of hybrid reactions 0.3h of temperature, with extruder in temperature
145 DEG C of extruding pelletizations, obtain impact modifier；
(3) 33 parts of hydroxyl dimethyl silicone polymers are weighed and 45 parts of amino silanes is added in closed container, anti-at 25 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 9 parts of APTESs, 8 parts of stearic acid, 17 parts of melamine trees are weighed
Fat is added in mill, with mill in 120 DEG C of hybrid reactions 0.2h of temperature, with extruder in 120 DEG C of extruding pelletizations of temperature,
Modified nano calcium carbonate is obtained, and the particle diameter of the modified nano calcium carbonate is 60nm, and oil factor is 10g/100g；
(5) 100 parts of polyvinyl chloride, 15 parts of modified nano calcium carbonates, 8 parts of vinyl bis-stearamides, 4 parts of nitrogen silicon resistances are weighed
Combustion agent, 10 parts of impact modifiers, 1 part of castor oil acid calcium, 5 parts of organic tin stabilizers and 3 parts of antioxidant mix in a kettle.
After even, it is transferred in mill, with mill in 145 DEG C of hybrid reactions 0.5h of temperature, is extruded into for 145 DEG C in temperature with extruder
Type, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 3
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 39 parts of N, N- diphenyl-para-phenylene diamines, 25 parts of ethanol and 62 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 60r/min, 0.7h is reacted under the conditions of 82 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 37 parts of nano titanium oxides, 25 parts of nano aluminium oxides, 92 parts of chlorinated polyethylenes are weighed
Alkene and 93 parts of mica powders are added in mill, with mill in 170 DEG C of hybrid reactions 1h of temperature, with extruder in temperature 170
DEG C extruding pelletization, obtains impact modifier；
(3) 45 parts of hydroxyl dimethyl silicone polymers are weighed and 35 parts of amino silanes is added in closed container, anti-at 35 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 17 parts of APTESs, 25 parts of stearic acid, 30 parts of melamines are weighed
Resin is added in mill, with mill in 175 DEG C of hybrid reactions 0.8h of temperature, is made in 175 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 70nm, and oil factor is 16g/100g；
(5) 100 parts of polyvinyl chloride, 30 parts of modified nano calcium carbonates, 15 parts of vinyl bis-stearamides, 17 parts of nitrogen silicon are weighed
Fire retardant, 23 parts of impact modifiers, 5 parts of castor oil acid calcium, 1 part of organic tin stabilizer and 8 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 220 DEG C of hybrid reactions 1h of temperature, is extruded into for 220 DEG C in temperature with extruder
Type, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 4
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 24 parts of N, N- diphenyl-para-phenylene diamines, 22 parts of ethanol and 47 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 49r/min, 0.5h is reacted under the conditions of 81 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 29 parts of nano titanium oxides, 24 parts of nano aluminium oxides, 91 parts of chlorinated polyethylenes are weighed
Alkene and 78 parts of mica powders are added in mill, with mill in 160 DEG C of hybrid reactions 0.7h of temperature, with extruder in temperature
160 DEG C of extruding pelletizations, obtain impact modifier；
(3) 35 parts of hydroxyl dimethyl silicone polymers are weighed and 39 parts of amino silanes is added in closed container, anti-at 32 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 16 parts of APTESs, 10 parts of stearic acid, 20 parts of melamines are weighed
Resin is added in mill, with mill in 130 DEG C of hybrid reactions 0.5h of temperature, is made in 130 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 68nm, and oil factor is 11g/100g；
(5) 100 parts of polyvinyl chloride, 20 parts of modified nano calcium carbonates, 10 parts of vinyl bis-stearamides, 13 parts of nitrogen silicon are weighed
Fire retardant, 15 parts of impact modifiers, 4 parts of castor oil acid calcium, 2 parts of organic tin stabilizers and 6 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 150 DEG C of hybrid reactions 0.8h of temperature, with extruder in 150 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 5
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 25 parts of N, N- diphenyl-para-phenylene diamines, 18 parts of ethanol and 45 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 48r/min, 0.4h is reacted under the conditions of 75 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 27 parts of nano titanium oxides, 19 parts of nano aluminium oxides, 85 parts of chlorinated polyethylenes are weighed
Alkene and 79 parts of mica powders are added in mill, with mill in 160 DEG C of hybrid reactions 0.8h of temperature, with extruder in temperature
160 DEG C of extruding pelletizations, obtain impact modifier；
(3) 39 parts of hydroxyl dimethyl silicone polymers are weighed and 43 parts of amino silanes is added in closed container, anti-at 34 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 14 parts of APTESs, 16 parts of stearic acid, 23 parts of melamines are weighed
Resin is added in mill, with mill in 140 DEG C of hybrid reactions 0.7h of temperature, is made in 140 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 61nm, and oil factor is 15g/100g；
(5) 100 parts of polyvinyl chloride, 24 parts of modified nano calcium carbonates, 13 parts of vinyl bis-stearamides, 9 parts of nitrogen silicon are weighed
Fire retardant, 17 parts of impact modifiers, 2 parts of castor oil acid calcium, 3 parts of organic tin stabilizers and 5 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 210 DEG C of hybrid reactions 0.7h of temperature, with extruder in 210 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 6
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 34 parts of N, N- diphenyl-para-phenylene diamines, 21 parts of ethanol and 57 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 53r/min, 0.4h is reacted under the conditions of 77 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 35 parts of nano titanium oxides, 22 parts of nano aluminium oxides, 86 parts of chlorinated polyethylenes are weighed
Alkene and 84 parts of mica powders are added in mill, with mill in 165 DEG C of hybrid reactions 0.8h of temperature, with extruder in temperature
165 DEG C of extruding pelletizations, obtain impact modifier；
(3) 38 parts of hydroxyl dimethyl silicone polymers are weighed and 36 parts of amino silanes is added in closed container, anti-at 26 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 14 parts of APTESs, 24 parts of stearic acid, 23 parts of melamines are weighed
Resin is added in mill, with mill in 168 DEG C of hybrid reactions 0.3h of temperature, is made in 168 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 64nm, and oil factor is 13g/100g；
(5) 100 parts of polyvinyl chloride, 21 parts of modified nano calcium carbonates, 14 parts of vinyl bis-stearamides, 11 parts of nitrogen silicon are weighed
Fire retardant, 17 parts of impact modifiers, 5 parts of castor oil acid calcium, 4 parts of organic tin stabilizers and 4 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 200 DEG C of hybrid reactions 0.7h of temperature, with extruder in 200 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 7
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 31 parts of N, N- diphenyl-para-phenylene diamines, 18 parts of ethanol and 47 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 52r/min, 0.5h is reacted under the conditions of 76 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 29 parts of nano titanium oxides, 23 parts of nano aluminium oxides, 86 parts of chlorinated polyethylenes are weighed
Alkene and 86 parts of mica powders are added in mill, with mill in 157 DEG C of hybrid reactions 0.9h of temperature, with extruder in temperature
157 DEG C of extruding pelletizations, obtain impact modifier；
(3) 45 parts of hydroxyl dimethyl silicone polymers are weighed and 44 parts of amino silanes is added in closed container, anti-at 27 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 13 parts of APTESs, 11 parts of stearic acid, 19 parts of melamines are weighed
Resin is added in mill, with mill in 158 DEG C of hybrid reactions 0.7h of temperature, is made in 158 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 69nm, and oil factor is 14g/100g；
(5) 100 parts of polyvinyl chloride, 29 parts of modified nano calcium carbonates, 12 parts of vinyl bis-stearamides, 16 parts of nitrogen silicon are weighed
Fire retardant, 22 parts of impact modifiers, 3 parts of castor oil acid calcium, 2 parts of organic tin stabilizers and 4 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 190 DEG C of hybrid reactions 0.9h of temperature, with extruder in 190 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 8
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 34 parts of N, N- diphenyl-para-phenylene diamines, 21 parts of ethanol and 46 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 51r/min, 0.3h is reacted under the conditions of 79 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 34 parts of nano titanium oxides, 21 parts of nano aluminium oxides, 88 parts of chlorinated polyethylenes are weighed
Alkene and 76 parts of mica powders are added in mill, with mill in 161 DEG C of hybrid reactions 0.4h of temperature, with extruder in temperature
161 DEG C of extruding pelletizations, obtain impact modifier；
(3) 36 parts of hydroxyl dimethyl silicone polymers are weighed and 39 parts of amino silanes is added in closed container, anti-at 33 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 11 parts of APTESs, 16 parts of stearic acid, 26 parts of melamines are weighed
Resin is added in mill, with mill in 157 DEG C of hybrid reactions 0.5h of temperature, is made in 157 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 63nm, and oil factor is 12g/100g；
(5) 100 parts of polyvinyl chloride, 18 parts of modified nano calcium carbonates, 12 parts of vinyl bis-stearamides, 6 parts of nitrogen silicon are weighed
Fire retardant, 17 parts of impact modifiers, 5 parts of castor oil acid calcium, 2 parts of organic tin stabilizers and 5 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 170 DEG C of hybrid reactions 0.9h of temperature, with extruder in 170 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 9
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 25 parts of N, N- diphenyl-para-phenylene diamines, 23 parts of ethanol and 47 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 51r/min, 0.6h is reacted under the conditions of 76 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 33 parts of nano titanium oxides, 22 parts of nano aluminium oxides, 84 parts of chlorinated polyethylenes are weighed
Alkene and 89 parts of mica powders are added in mill, with mill in 164 DEG C of hybrid reactions 0.6h of temperature, with extruder in temperature
164 DEG C of extruding pelletizations, obtain impact modifier；
(3) 42 parts of hydroxyl dimethyl silicone polymers are weighed and 43 parts of amino silanes is added in closed container, anti-at 34 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 12 parts of APTESs, 20 parts of stearic acid, 26 parts of melamines are weighed
Resin is added in mill, with mill in 137 DEG C of hybrid reactions 0.7h of temperature, is made in 137 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 62nm, and oil factor is 13g/100g；
(5) 100 parts of polyvinyl chloride, 18 parts of modified nano calcium carbonates, 11 parts of vinyl bis-stearamides, 8 parts of nitrogen silicon are weighed
Fire retardant, 16 parts of impact modifiers, 2 parts of castor oil acid calcium, 4 parts of organic tin stabilizers and 4 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 160 DEG C of hybrid reactions 0.8h of temperature, with extruder in 160 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Embodiment 10
A kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing, its preparation method are comprised the following steps：
(1) 100 parts of trisnonyl phenyl phosphites, 26 parts of N, N- diphenyl-para-phenylene diamines, 23 parts of ethanol and 54 parts of oxygen are weighed
Change aluminium to be added in reactor, mixing speed is 49r/min, 0.5h is reacted under the conditions of 78 DEG C of maintenance system temperature, obtain antioxygen
Agent；
(2) 100 parts of ethylene propylene diene rubbers, 28 parts of nano titanium oxides, 19 parts of nano aluminium oxides, 86 parts of chlorinated polyethylenes are weighed
Alkene and 77 parts of mica powders are added in mill, with mill in 152 DEG C of hybrid reactions 0.8h of temperature, with extruder in temperature
152 DEG C of extruding pelletizations, obtain impact modifier；
(3) 38 parts of hydroxyl dimethyl silicone polymers are weighed and 37 parts of amino silanes is added in closed container, anti-at 25 DEG C
10min is answered, after material is well mixed, is mixed during added 10 parts of magnesium hydroxides to reactor
12min, that is, obtain nitrogenated silicon fire retardant；
(4) 100 parts of nano-calcium carbonates, 13 parts of APTESs, 14 parts of stearic acid, 25 parts of melamines are weighed
Resin is added in mill, with mill in 128 DEG C of hybrid reactions 0.3h of temperature, is made in 128 DEG C of extrusions of temperature with extruder
Grain, that is, obtain modified nano calcium carbonate, and the particle diameter of the modified nano calcium carbonate is 66nm, and oil factor is 15g/100g；
(5) 100 parts of polyvinyl chloride, 17 parts of modified nano calcium carbonates, 13 parts of vinyl bis-stearamides, 5 parts of nitrogen silicon are weighed
Fire retardant, 16 parts of impact modifiers, 5 parts of castor oil acid calcium, 1 part of organic tin stabilizer and 6 parts of antioxidant mix in a kettle.
After uniform, it is transferred in mill, with mill in 180 DEG C of hybrid reactions 0.7h of temperature, with extruder in 180 DEG C of extrusions of temperature
Shaping, that is, obtain abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics tubing.
Reference examples 1
In this reference examples, from the nitrogen silicon fire retardant in ammonium polyphosphate flame retardant alternate embodiment 1 in formulating of recipe for pipes, other
Component is same as Example 1 with preparation method.
Reference examples 2
In this reference examples, the modified nano calcium carbonate in formulating of recipe for pipes is by nano-calcium carbonate, 3- aminopropyl triethoxies
Silane is constituted, and the preparation method of modified nano calcium carbonate is：
Weigh 100 parts of nano-calcium carbonates and 13 parts of APTESs are added in reactor, in temperature
80 DEG C of hybrid reactions 0.5h, that is, obtain modified nano calcium carbonate.
Other components in this reference examples are same as Example 1 with preparation method.
Reference examples 3
In this reference examples, the oil factor of the modified nano calcium carbonate in formulating of recipe for pipes is 70g/100g, in this reference examples
Other components are same as Example 1 with preparation method.
To embodiment 1～10 and abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics pipe obtained in reference examples 1～3
The performance such as wear-resisting, fire-retardant of material is tested, and method of testing is as follows, and test result see the table below 1.
(1) anti-wear performance
Tested by the wear-resisting level estimate standards of EN660-2；
(2) oxygen index (OI)
Press GB/T2406.2-2009/ISO4589-2:1996 standards are tested；
(3) drop impact performance
Tested by GB/T14152-2001 standards；
(4) tensile strength
Press MT 558.2-2005 plastic pipe for coal mine material part 2s：Polychloroethylene pipes
1 embodiment 1～10 of table and abrasion resistant fire blocking environment-friendly polyvinyl chloride/nanometer calcium carbonate plastics pipe obtained in reference examples 1～3
The performance measurement of material
Wear-resisting hierarchal order is T level ＞ P level ＞ M level ＞ F levels, and from upper table 1, various embodiments of the present invention are prepared
Tubing wear-resisting higher ranked, this shows, with the tubing for preparing of raw material that the present invention is provided, there is preferable anti-wear performance；
By contrast, the anti-wear performance of the tubing that the raw material of each reference examples is prepared is poor.In addition, various embodiments of the present invention are prepared into
To tubing there is preferable fire resistance and mechanical property.
Claims (10)
1. a kind of abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing, it is characterised in that mass parts pressed by the tubing
Number is made up of following raw material：
100 parts of polyvinyl chloride；
15～30 parts of modified nano calcium carbonate；
8～15 parts of vinyl bis-stearamides；
4～17 parts of nitrogen silicon fire retardant；
10～23 parts of impact modifier；
1～5 part of castor oil acid calcium；
1～5 part of organic tin stabilizer；
3～8 parts of antioxidant；
Wherein, the modified nano calcium carbonate is by nano-calcium carbonate, APTES, stearic acid, melamine tree
Fat reaction is obtained；The oil factor of the modified nano calcium carbonate is 10～20g/100g.
2. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 1, it is characterised in that described
The oil factor of modified nano calcium carbonate is 10～16g/100g.
3. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 1, it is characterised in that described
The particle diameter of modified nano calcium carbonate is 50～100nm.
4. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 1, it is characterised in that described
Nano-calcium carbonate, APTES, stearic acid, the mass ratio of melamine resin are 100：9～17：8～25：17
～30.
5. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 4, it is characterised in that described
The preparation method of modified nano calcium carbonate is：
During nano-calcium carbonate, stearic acid, melamine resin are added successively to APTES, to be mixed uniform
After transfer the material in mill, at a temperature of 120～175 DEG C react 0.2～0.8h, then use extruder extruding pelletization,
Obtain final product modified nano calcium carbonate.
6. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 1, it is characterised in that described
Nitrogen silicon fire retardant is made up of magnesium hydroxide, hydroxyl dimethyl silicone polymer, amino silane.
7. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 6, it is characterised in that described
In nitrogen silicon fire retardant, the mass ratio of magnesium hydroxide, hydroxyl dimethyl silicone polymer and amino silane is 10：33～45：35～45.
8. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 1, it is characterised in that described
Impact modifier is obtained by the reaction of ethylene propylene diene rubber, nano titanium oxide, nano aluminium oxide, haloflex and mica powder.
9. abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing according to claim 1, it is characterised in that described
Antioxidant is obtained by trisnonyl phenyl phosphite, N, N- diphenyl-para-phenylene diamines, ethanol and oxidation reactive aluminum.
10. the preparation method of abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing described in claim 1～9, its are special
Levy and be, methods described comprises the steps：
S1：During nano-calcium carbonate, stearic acid, melamine resin are added successively to APTES, to be mixed
Transfer the material in mill after uniform, 0.2～0.8h is reacted at a temperature of 120～175 DEG C, then made with extruder extrusion
Grain, obtains final product modified nano calcium carbonate；
S2：It is well mixed during modified nano calcium carbonate and other materials are added to reactor, then transfers the material into mill
In machine, 0.5～1h of hybrid reaction under the conditions of 145～220 DEG C, and extrusion molding under the conditions of 145～220 DEG C, obtain final product described
Abrasion resistant fire blocking environment-friendly polyvinyl chloride nanometer calcium carbonate plastics tubing.
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| CN108504001A (en) * | 2018-06-29 | 2018-09-07 | 钦州市宝业坭兴陶厂 | A kind of modified calcium carbonate filled PVC tubing and preparation method thereof |
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